EP0074435B1 - Verfahren und Apparat zur Kohlenwasserstoffspaltung; Mischanlage; Apparat und Verfahren zur Produktion von überhitztem Dampf; Radiationblockstruktur - Google Patents

Verfahren und Apparat zur Kohlenwasserstoffspaltung; Mischanlage; Apparat und Verfahren zur Produktion von überhitztem Dampf; Radiationblockstruktur Download PDF

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Publication number
EP0074435B1
EP0074435B1 EP81201000A EP81201000A EP0074435B1 EP 0074435 B1 EP0074435 B1 EP 0074435B1 EP 81201000 A EP81201000 A EP 81201000A EP 81201000 A EP81201000 A EP 81201000A EP 0074435 B1 EP0074435 B1 EP 0074435B1
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EP
European Patent Office
Prior art keywords
hydrocarbon
conduit
steam
superheated steam
process according
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81201000A
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English (en)
French (fr)
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EP0074435A2 (de
EP0074435A3 (en
Inventor
Peter Hubertus Kösters
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Dow Chemical Nederland BV
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Dow Chemical Nederland BV
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Priority to EP81201000A priority Critical patent/EP0074435B1/de
Priority to DE8181201000T priority patent/DE3173374D1/de
Priority to US06/405,212 priority patent/US4426278A/en
Priority to CA000423303A priority patent/CA1207266A/en
Priority to JP58044584A priority patent/JPS59170187A/ja
Priority to AU12624/83A priority patent/AU556528B2/en
Publication of EP0074435A2 publication Critical patent/EP0074435A2/de
Publication of EP0074435A3 publication Critical patent/EP0074435A3/en
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Publication of EP0074435B1 publication Critical patent/EP0074435B1/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/40—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by indirect contact with preheated fluid other than hot combustion gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • This invention relates to a process and an apparatus for cracking hydrocarbon.
  • the invention also relates to a radiation block structure, suitable for use in such processes.
  • the cracking reaction takes place in a plurality of individual suspended tubes, positioned within a large firebox.
  • a furnace may require over 100 burners, which are generally mounted on the walls of the firebox, to transfer sufficient heat through the reactor tubes to the hydrocarbon.
  • One disadvantage is that all of the reactor tubes are exposed to the same flue gas temperature. Therefore, the maximum heat flux is limited by the maximum metal break-down temperature of the reactor tube.
  • overheating can cause undesirable reactions such as the formation of an undesirable high methane content in the final product and an increase in the build-up of coke deposits on the inside of the reactor tubes. For these reasons, a relatively low average heat flux is required over the length of the reactor tubes.
  • the reactor tubes in a conventional cracking furnace are necessarily from about 50 to about 100 meters long. This is undesirable because the residence time of the hydrocarbons in the reaction zone is significantly longer than optimum and the pressure drop through each tube is undesirably high.
  • British patent specification No. 560,195 describes a process for cracking hydrocarbon oils to produce lower boiling unsaturated hydrocarbons by vaporising the heavy hydrocarbon oil, adding superheated steam to the vapourising oil, separating off condensed water and unvapourised oil the resulting mixture and passing the vapourised oil and steam mixture through a box-type furnace.
  • the described process which is employed to reduce the viscosity of the heavy hydrocarbon oils, exhibits the same inherent disadvantages as described.
  • This process also has several disadvantages. For example, it requires mixing tars and heavy fuel oils with oxygen to generate the burner flame for the cracking reaction. Because the cracking reaction takes place in the flame, the heavier hydrocarbons are mixed with the hydrocarbon in the cracking zone, and the final product thus contains undesirable products, for example methane.
  • this process is a fully "adiabatic" operation, in which heat for the cracking reaction is supplied only by the partially burned carrier gases and steam. To supply enough heat for the reaction, the gases must be heated to very high temperatures (over 1600°C) and the ratio of carrier gases to the hydrocarbon must, of necessity, be high.
  • the process according to the invention for cracking hydrocarbon is characterized by mixing the hydrocarbon with superheated steam, passing the resulting mixture through a reactor conduit extending through a radiation block structure, heating the mixture of hydrocarbon and superheated steam while flowing heating gas through the radiation block structure co-current with the flow of hydrocarbon through the reactor conduit and passing the hot reaction product from the reactor content into a heat exchanger for quenching the reaction product.
  • the heat required for the cracking reaction is provided partially adiabatic by means of superheated steam and partially by indirect heating with hot gases. Therefore, an optimal temperature profile in the reaction zone is achieved.
  • the present process provided an essentially immediate start of the cracking reactions, a relatively high heat flux at the places where the endothermic pyrolysis reactions require this and a continuous lower heat flux as the cracking reaction proceeds. By rapidly cooling the reaction product, undesirable secondary reactions are reduced. Therefore, by the process of the present invention, relative high ethylene yields can be obtained.
  • the steam in the superheated steam production and reaction zone is exposed to a relatively low pressure drop, e.g. less than about 4 atmospheres (atm.), preferably less than about 1 atm.
  • steam having a pressure of only a few atmospheres e.g., from about 2 to 12 atmospheres can be employed.
  • the invention also provides for the possibility of good on-line cleaning of parts subject to fouling, e.g. by coke depositions, in a very short period of time. As compared with conventional processes, in which lengthy cleaning with manpower is required, this means a considerable saving in time and manpower.
  • the apparatus according to the invention for cracking hydrocarbon is characterized by a means for producing superheated steam, a mixing device for mixing the hydrocarbon with the superheated steam, a reactor conduit through which the mixture of hydrocarbon and superheated steam can flow, said reactor conduit extending through a radiation block structure, provided with a passage which allows the flow of gases around at least a portion of the reactor conduit, means for heating the mixture of hydrocarbon and superheated steam, which means provides for the flow of heating gases through the radiation block structure, and a heat exchanger for quenching the hot reaction product.
  • the radiation block structure according to the present invention is characterized by a plurality of abutting blocks of ceramic material forming an elongated passage having (a) an aperture through which a conduit can be passed and (b) open spaces in communication with said conduit aperture, said spaces having such a configuration as to form passage for a gas.
  • the hydrocarbon cracking apparatus of this invention comprises a heat recovery apparatus F, which is preferably but optionally employed, a steam superheater S and a reaction zone R.
  • Steam superheater unit S contains a steam conduit 16 for carrying superheated steam to a mixing device 13 for mixing with the hydrocarbon feed.
  • a first header 17 for receiving steam at a relatively low temperature.
  • the steam is distributed by means of a plurality of convection heat conduits 18 (three being shown in Fig. 1).
  • the conduits 18 are generally provided with a plurality of fins. From conduits 18, the superheated steam flows through a second header 19 and into steam conduit 16. The flow of the superheated steam is indicated by numeral 32.
  • the steam line 16 is positioned inside a passage provided in a radiation block structure 22, one end of which opens into a chamber 23, which allows the flow of heating gas, e.g., hot combustion or flue gas, from a burner nozzle 24 through the radiation block structure 22 in a direction countercurrent to the steam in line 16, as indicated by the flow path 20.
  • heating gas e.g., hot combustion or flue gas
  • the heating gases flow over and around convection heat conduits 18 and are then discharged through stack 21.
  • the gas flow path is indicated by numeral 20.
  • the steam line 16 is positioned inside the passage provided in a similar radiation block structure 25.
  • the end of this radiation block structure away from mixing device 13 opens into another chamber 26.
  • heating gas from a burner nozzle 27 flows through chamber 26 and the passageway in the radiation block co-currently with the flow of the steam in line 16, as indicated by the flow path 28.
  • the temperature of the heating gas is at a maximum when the steam is at a relatively low temperature with said temperature decreasing as the temperature of the steam increases.
  • the optimum heat flux is maintained without the possibility of overheating the steam conduit.
  • the heating gases pass through a duct 30 into the convection section 10 and are thereafter discharged through stack 11.
  • the optionally employed heat recovery apparatus F contains a convection section 10 and a stack 11 for carrying heating gases out of the convection section.
  • a hydrocarbon feed line 12 which carries the hydrocarbon to the mixing device 13 passes through the convection section 10.
  • the hydrocarbon Prior to mixing the hydrocarbon with the superheated steam, in general the hydrocarbon is preferably pre-heated in the heat recovery apparatus 10 to a temperature and at conditions such that the hydrocarbon is converted to a vapor or fine mist without significant cracking of the hydrocarbon feed.
  • preheating is not required to convert the hydrocarbon to a vapor or fine mist but serves merely as a means of energy recovery.
  • the hydrocarbon is preferably not pre-heated when unsaturated or very heavy hydrocarbons are to be cracked.
  • the hydrocarbon feed is mixed with water or steam prior to or coincident with such pre-heating.
  • the hydrocarbon is preferably mixed with liquid water prior to preheating.
  • the hot gases employed in preparing the superheated steam and heating the reacting mixture to their desired temperature are preferably employed in pre-heating the hydrocarbon feed.
  • Numeral 31 indicates the flow path of the hydrocarbon as it passes through the heat recovery apparatus 10 to mixing device 13. Inside of mixing device 13, the hydrocarbon is mixed with the superheated steam.
  • reaction zone R consists of a reactor conduit 34 extending through a radiation block structure 35, preferably extending substantially horizontally therethrough.
  • the end of the radiation block structure 36 nearest mixing device 13 opens into a chamber 36, preferably located in close proximity to the mixing device.
  • the mixture of hydrocarbon and superheated steam from mixing device 13 passes into reactor conduit 34 with the flow of the hydrocarbon/superheated steam mixture being indicated by numeral 39.
  • the cracking reactions start immediately at a high rate. Because of the strong endothermicity of these pyrolysis reactions this results in a temperature decrease of the reacting mixture. Due to this temperature decrease, it is possible to supply heat with a very high flux at the inlet of the reactor tube. Therefore, the mixture of hydrocarbon and superheated steam is passed, preferably immediately upon mixing, through chamber 36.
  • the heating gases 38 from a burner 37 flow through chamber 36 and a passageway in the radiation block structure in a direction co-current to the flow of the hydrocarbon/superheated steam mixture through reactor conduit 34.
  • the reaction rates, as well as the heat uptake diminish.
  • the reduction in the temperature of the heating gas as it flows through the radiation block structure in a direction co-current with the flow of the hydrocarbon results in a reduction of the heat flux along the length of the reactor conduit.
  • This mode of operation can be defined as "continuous profile firing".
  • the heat flux can also be partially controlled by using radiation blocks having a larger or smaller interior surface area.
  • the resulting reaction product is discharged directly into a primary heat exchanger 47 which provides for fast cooling of the reaction product.
  • a primary heat exchanger 47 Inside the heat exchanger 47, the hot reaction product passes through the shell side of the heat exchanger and makes indirect contact with a lower temperature fluid, preferably water, passing through the tube side of the exchanger.
  • the lower temperature fluid enters the exchanger through inlet 48 and exits through outlet 49.
  • the cooled product then passes from exchanger 47 through a product outlet conduit 50, optionally, into one or more additional heat exchangers where the product is further cooled and the steam in the product stream is condensed. Subsequently the product can be recovered.
  • the hydrocarbon is mixed with water or steam and the hydrocarbon subsequently preheated to a desired temperature generally from 300°C-700°C, as it flows through feed line 12 passing through the heat recovery apparatus 10.
  • the amount of steam or water to be admixed with the hydrocarbon feed and the temperature to which the mixture is pre-heated is dependent on the composition of the feed.
  • the feed consists of light hydrocarbons, (e.g.
  • hydrocarbon feed containing primarily hydrocarbons of 5 or less carbon atoms little or no water, preferably less than about 20% by weight, based on the weight of the hydrocarbon, is added and the mixture is pre-heated to approximately 500-700°C.
  • heavy hydrocarbons e.g., a hydrocarbon feed containing primarily hydrocarbons of 6 or more carbon atoms
  • water is added, and the mixture is pre-heated to approximately 300-500°C.
  • the hydrocarbon is typically a vapor or exists as fine droplets of hydrocarbon dispersed in steam (indicated herein as a mist).
  • the desired temperature is obtained by pre-heating the hydrocarbon using the heating gases employed in heating the superheated steam and reacting mixture. These gases which move upwardly through the convection section 10 and are discharged through stack 11 typically have a temperature of from 1000° to 1200°C.
  • Steam typically enters header 17 at from 100°-200°C and an absolute pressure from 1 to 12, preferably 2 to 5, atm.
  • the heating gases 20 moving countercurrently to the steam, 'at a temperature typically from 600°-1000°C, preferably from 700°-900°C, add further heat such that the steam in the second header 19 typically reaches 400 to 600°C.
  • the steam pressure at this point is generally from 0,8 to 10 atm. and slightly less than the steam pressure at header 17.
  • the heating gas temperature is typically from 1400° to 2000°C, preferably from 1500° to 1700°C, the higher temperatures being generally employed when the steam conduit is made of a ceramic material.
  • the heating gas 20 moves in a countercurrent flow to the steam in conduit 16 through the first heating zone of the steam superheater S between header 19 and chamber 23, its temperature gradually drops to from about 600° to about 1000°C at header 19, and to from 150° to 250°C as it passes through the stack 21.
  • the transfer of heat to the steam causes the steam temperature typically to rise to from about 700° to 1000°C, at chamber 23.
  • the temperature of the heating gas is typically from 1400° to 2000°C, preferably from 1500° to 1700°C.
  • the heating gas 28 moves co-currently. with superheated steam in line 16 through the second heating zone of the steam superheater S between chamber 26 and mixing device 13, the heating gas temperature typically drops to from 1000° to 1700°C at the mixing device 13 and the steam is further heated to from 1000° to 1500°C.
  • steam of 1100-1400°C is preferred.
  • the steam pressure at the mixing device is from 0,8 to 5 atm., more typically from 1 to 3 atm. A length of 30 meter (m) and even shorter will suffice for the steam conduit 16. The shorter the steam line, the less is the pressure drop.
  • the pre-heated hydrocarbon is admixed with the superheated steam.
  • the temperature and amounts of superheated steam employed raise the temperature of the hydrocarbon to from 700°-1000°C. This rise in temperature of the hydrocarbon is caused by an almost instantaneous mixing of the hydrocarbon with the superheated steam from steam line 16. This temperature rise therefore enables the cracking reaction to start at the very instant the reaction mixture enters the front end of the reactor conduit.
  • the mixture is heated by gases from burner 37.
  • the heating gases generated by burner 37 have a temperature from 1700° to 2000°C, preferably 1750-1850 0 C.
  • the superheated steam/hydrocarbon moves rapidly through conduit 34.
  • the desired residence time in conduit 34 depends on a variety of factors including the composition of the hydrocarbon feed, the reaction (cracking) temperatures and the desired reaction products.
  • the desired residence time for a heavy hydrocarbon feed in the reaction zone i.e., from mixing device to heat exchanger, is from 0,005 to 0,15, preferably 0,01 to 0,08 seconds.
  • the residence time in the reactor conduit for a light hydrocarbon is preferably 0,03-0,15 seconds.
  • the temperature of the heating gas typically drops to from 1000 to 1300°C at the point where the heating gas enters the outlet duct 51.
  • the heat supplied by the heating gas is a combination of heat by radiation and by convection. For example, about 90 percent of the heat supplied to the reactor conduit 34 is by radiation from the radiation block structure while the remaining part is by convection and radiation from the heating gas.
  • the heat supplied direct from the heating gas to the reactor tube is about 4 percent radiant heat and 6 percent convection heat (percent of total heat flux).
  • the excellent heat transfer by radiation from the blocks is made possible by the extended surface area of the longitudinal passage in the radiation block structures.
  • the temperature of the reaction product varies from 700° ⁇ 1000°C throughout the reactor conduit 34.
  • part of the heat required for the reaction is supplied adiabatically by the sensible heat of the superheated steam while another part of the reaction heat is supplied by the heating gas which pass through radiation blocks and simultaneously heats both the blocks and the reactor conduit.
  • the highest heat flux required for the reaction is supplied at the exact point needed, that is immediately upon mixing the superheated steam and hydrocarbon (at which point the heating gas has a temperature of about 1850°C). At this point cracking reactions proceed at the highest rate, so that cooling by the endotherm effect of the reactions is maximal. For this reason very high heat fluxes are possible in the first part of the reactor tube, without exceeding the maximum tube wall temperature (skin temperature).
  • the heating gas gradually cools from about 1850°C at the burner to a temperature from 1000-1300°C at the outlet where the heating gas is discharged into the duct 51. Cooling of the heating gas prevents the skin temperature of the reactor tube from exceeding the maximum requirement, for example, about 1100°C.
  • the reaction product enters the primary heat exchanger 47, on the shell side, and is immediately cooled, for example to a temperature of about 350-750°C, by a lower temperature fluid, preferably water, which is flowing through the tube side of the exchanger. This temperature is low enough to immediately stop the reactions leading to the formation of undesirable components.
  • the residence time in the heat exchanger is preferably no longer than about 0,03 seconds.
  • water is employed as the lower temperature fluid, the water is vaporized to form relatively high pressure steam by the heat transferred from the reaction product.
  • the primary heat exchanger, identified by 47 in Fig. 1, is illustrated only schematically and described only generally herein. A preferred heat exchanger is described in detail in copending Patent Application, Ser. No. filed .
  • the reaction product After cooling in the primary heat exchanger 47, the reaction product is discharged through the product outlet 50 and generally pressed through one or more additional. heat exchangers or quenchers (not shown) connected to the heat exchanger 47. As it passes through these heat exchangers or quenchers, the product is further cooled. Cooling in a heat exchanger can be accompanied by generation of steam due to vaporization of water which is generally used as cooling medium. Condensation of the steam mixed with the hydrocarbon reaction product can result in the production of relatively low pressure steam which can be effectively re-employed for producing superheated steam. Further downstream the final product is recovered as a hydrocarbon composition which can contain a high proportion of ethylene.
  • Hydrocarbon pyrolysis reactions can cause substantial build up of coke deposits in the reactor tubes or conduits in a relatively short time.
  • the hydrocarbon feed to the mixing device 13 is shut off.
  • the inlet 48 and the outlet 49 in the primary heat exchanger 47 are closed.
  • Accumulated fluid remaining in the tubes of the primary exchanger is drained.
  • superheated steam only typically at about 1000-1100°C, is passed from the superheater unit S through the steam line 16, mixing device 13, the reactor conduit 34, and into the primary heat exchanger 47.
  • the high temperature steam passes through the reactor conduit 34, and the shell side of the primary heat exchanger 47, it removes coke deposits within the reactor conduits, as well as coke deposits on the outside of the tubes in the heat exchanger and the inside of the shell housing.
  • the hot steam flows out of the product outlet 50 and possibly through one or more additional heat exchangers or quenchers (not shown) downstream of the primary heat exchanger 47.
  • the hot steam may be cooled by injecting water through a valve 52. The steam is cooled at this point to avoid damaging the tube structure in the secondary heat exchanger since the upper temperature limit for these tubes is generally about 500°C.
  • This decoking operation provides distinct advantages over the decoking/cleaning techniques conventionally employed for decoking/cleaning hydrocarbon cracking reactors.
  • Conventional decoking procedures usually require shutting off the hydrocarbon feed and running high temperature air (400-800°C) through the reactor for at least 24 hours to remove the coke. Since the furnace temperature is reduced significantly during this conventional cleaning operation, the metal of the reactor conduits and the furnace brickwork may be severely damaged as a result of material contraction.
  • the exothermicity of an oxygen coke reaction may cause local hot spots and material damage.
  • the decoking of the cracking reactor of this invention is an on-line decoking operation, in which only the hydrocarbon feed needs to be shut off.
  • the whole procedure can be done in a short time, for example, about 1 to 6 hours.
  • the reactor conduit remains at cracking temperatures, so that there is no damage from thermal cycling. Because of the endothermicity of the steam-decoke reaction, there is no risk of overheating materials.
  • coke deposits are removed from the inside of the reactor conduit 34 and, in the same operation, from the outside of the tubes and the inside wall of the shell housing in the primary heat exchanger 47 without having to shut the system completely down for the decoking operation.
  • FIG. 9 A different preferred embodiment of the present invention is depicted in Fig. 9, to be indicated herein as co-cracking.
  • the steam superheater unit S comprises a steam conduit 62, located in radiation block structure 63.
  • Heating gases originate from a hot gas generator 64.
  • the heating gas generator is positioned at the steam inlet side of superheater unit S.
  • the injection of fresh fuel and air, preferably pre-heated air, along steam conduit 62 adjusts the temperature of the heating gases to the desired value.
  • the stream of heating gases is entirely co-current with the stream of steam in the steam conduit 62.
  • the cracking reactor unit R comprises mixing devices 60 and 61, reactor tubes 73 and 74, and radiation blocks 65 and 66.
  • the temperature of the heating gases is increased, in the embodiment shown, to the desired value by the injection of fresh fuel and air, preferably pre-heated air, through fuel injectors 67 and 68.
  • the heating gases flow from radiation block structure 66 through conduits 70 to the convection section, from which they are discharged through stack 71.
  • discharge conduits (not shown) for the heating gases may be provided at places where the quantity of heating gases becomes too great, for example, upstream of the mixing devices, through which discharge conduits the heating gases can be passed to convection section 69.
  • the reaction conduit 74 is connected to heat exchanger 72 to allow reaction product to pass to the heat exchanger and be cooled.
  • a lighter hydrocarbon feed and a heavier hydrocarbon feed are supplied separately through supply conduit 58 and supply conduit 59, respectively.
  • the lighter hydrocarbon feed is preferably pre-heated to a desired temperature (e.g. from 500-700°C for a feed containing primarily hydrocarbons of 5 or less carbon atoms), and, optionally, admixed with a small quantity of water or steam.
  • This lighter feed is admixed in a first mixing device 60 with superheated steam, preferably having a temperature from 1000 to 1500°C, and more preferably from 1100 to 1400°C. The higher steam temperatures will result in larger quantities of acetylene being formed.
  • the heavier hydrocarbon feed is preferably pre-heated to a desired temperature and admixed with water or steam (e.g. heated to from 300-500°C and mixed with 10-70% by weight of water or steam, based on the weight of the heavy hydrocarbon feed for a feed containing primarily hydrocarbons of 6 or more carbon atoms).
  • water or steam e.g. heated to from 300-500°C and mixed with 10-70% by weight of water or steam, based on the weight of the heavy hydrocarbon feed for a feed containing primarily hydrocarbons of 6 or more carbon atoms.
  • the heavier hydrocarbon. is supplied at .a place downstream of the first mixing device by means of a second mixing device 61. This is advantageous because the heavier hydrocarbons need a lower cracking temperature and a shorter residence time in the reaction zone.
  • the hydrogen deficiency of the heavier hydrocarbons which results in the production of less ethylene, is compensated by the hydrogen transfer via radicals from the lighter hydrocarbon to the heavy hydrocarbon.
  • the hot cracking gas mixture is rapidly cooled, preferably within 0,03 sec., in heat exchanger 72. Decoking of the cracking reactor and primary heat exchanger is conducted in the manner as described herein before.
  • the radiation block structures in both the steam superheater S and the reaction zone R are similar.
  • a preferred radiation block structure is shown in Figs. 2 and 3 and a second preferred embodiment in Figs. 4 and 5.
  • the radiation block structure 35 consists of individual sections 40, each fitted tightly together by a suitable fastening means, such as a tongue and groove arrangement.
  • a passage 41 extending through the block structure illustrated by Fig. 2 has a configuration, in cross-section, of a four-leaf clover.
  • the centre of the passage 41 is defined by four inwardly extending projections defining inner shoulders 42.
  • the reactor conduit 34 is positioned in the passage 41 in such a manner that the tube is supported by at least one inner shoulder 42 of the radiation block.
  • the other shoulders 42 are spaced only a short distance from the outer wall surface of the conduit 34. The purpose of leaving this small space between the outer wall surface of the tube and some of the shoulders in the passage in the radiation block is to allow for creep and thermal expansion of the reactor conduit 34 under high temperature conditions.
  • the radiation block structure 35 consists of a plurality of individual sections 43. These pieces are also fitted tightly together by a suitable fastening means, such as a tongue and groove arrangement.
  • a spiral passage extends lengthwise through this radiation block structure and is defined by the adjoining spaces 44.
  • the outer limit of the passage is defined by an outside shoulder 45 in each of the spaces 44.
  • the centre of the passage is defined by inside shoulders 46, which join each of the spaces 44.
  • the passageway is formed by machining a four-helix opening through the radiation block structure.
  • the reactor conduit 34 in this preferred radiation block structure illustrated in Fig. 4 is also positioned in such a manner that the conduit is supported by the radiation block.
  • the outer wall surface of the conduit does not touch the inside shoulders 46 over the whole circumference of the tube.
  • a small space is provided between the conduit and the shoulders, as explained earlier, to make an allowance for creep and temperature expansion of the conduit during conditions of high temperature.
  • the radiation block structure serves to provide for a large heat flux.
  • Heat flux means the amount of heat transferred from the heating gas to the material within the conduit and can be expressed in kcal/hour/m 2 or watt/m 2 .
  • the direct heat transfer from the heating gases to the reaction conduit and the steam conduit is relatively slight.
  • a large heat flux can be achieved with radiant heat from the interior surface of the radiation blocks.
  • an interior surface of the radiation blocks can be provided which gives optimum heat flux. For example, higher heat flux can be provided by enlarging the surface area of the radiation block.
  • the radiation blocks near mixing device 13 may advantageously have a larger internal surface area than those at the opposite end of the reactor conduit.
  • the materials used in the construction of the radiation block structures in both the steam superheater unit and the reaction zone are those materials which are sufficiently heat resistant to withstand the temperatures being employed in the cracking operation.
  • Preferred materials are ceramic compositions of the type used in high temperature refractory materials.
  • a specific material used in fabricating these blocks is a ceramic composition consisting of relatively pure aluminum oxide with a chromium oxide additive to provide extra strength.
  • Other materials which may be used in the radiation block structures include magnesium oxide, zirconium oxide, thorium oxide, titanium oxide, silicon nitride, silicon carbide and oxide fibre materials.
  • the reactor conduit and superheated steam conduits are made of materials which can be produced in the desired shape, e.g., tubes, and which are sufficiently temperature resistant to withstand the temperatures of operation.
  • Metal compositions which may be used to fabricate the reactor conduits are Ni-based alloys of iron, chromium, cobalt, molybdenum, tungsten, and tantalum or reinforced Ni-metal or Ni-alloy tubes. These nickel-alloy compositions can withstand a high temperature of about 1200°C, and these compositions can also hold up under the pressure conditions inside the reactor conduit. Of such metal compositions,,alloys of nickel and chromium are preferred.
  • the reactor tube can preferably be fabricated of ceramic compositions such as AI z 0 3 , Si 3 N 4 , SiC and the like to enable temperatures higher than 1200°C, both corresponding higher heat fluxes, to be employed. This will enable a further reduction of residence time, so that a higher selectivity towards ethylene can be reached. Also material expansion problems at the high temperature of operation are substantially reduced.
  • these ceramic materials are transparent or translucent.
  • significant amounts of heat are transferred by radiation from the ceramic blocks and heating gas directly to the reacting mixture.
  • the reactor conduit will have a lower temperature while providing higher heat flux to the reacting mixture.
  • coking of the reactor conduit will be reduced.
  • the average length of the reactor conduit should be such that the residence time is no longer than 0,15 sec. Shorter conduits are preferred to provide the desired short residence time and a desired small pressure drop. A length of between 3 and 25 meters, preferably no longer than 15 meters is preferred.
  • the inside diameter of the reactor and superheated steam conduit can be of essentially any dimensions with the actual dimensions of the reactor conduit depending mostly on the composition of the hydrocarbon feed which is being cracked.
  • the reactor tube preferably has a length from 3 to 10 meters and has dimensions such that the residence time of the reaction mixture in the reactor conduit (the reaction zone) is from 0,005 to 0,08 seconds.
  • a reactor conduit will generally be a tube having an inside diameter from 20 to 300 millimeter (mm); with an inside diameter from 50 to 150, preferably 85 to 100 mm, being advantageously employed.
  • conduits are preferably contiguously supported in a horizontal position, whereby such problems are substantially overcome.
  • Another feature of this invention is the capability of utilizing a wide variety of fuels to superheat the steam and to provide heat for the cracking reaction.
  • the heating gases are produced by gas generators which can burn virtually any fuel, such as coal, lignite, heavy oils, tars and gases, such as methane, propane, butane and the like.
  • Another advantage of this invention over the known systems is the precise control of the burner nozzles in the heating gas generators. This gives a flame which is relatively pure, that is, it does not contain particles of unburned matter which can impinge on the reactor conduit and thus cause overheating of the conduit.
  • fuel to air ratio control is better than for conventional natural draft furnaces, where local differences in fuel to air ratio can occur, because of an incorrect setting of the individual burners.
  • the hydrocarbon and superheated steam are mixed at conditions such that the hydrocarbon is intimately mixed with the superheated steam without previously contacting a wall of the reactor conduit.
  • a preferred mixing device 13 comprises an elongated passage 14, defined by the interior walls of hydrocarbon delivery conduit 81, for the delivery of hydrocarbon for subsequent mixing with the superheated steam in a mixing bore 15.
  • the hydrocarbon delivery conduit 81 is preferably separated from a thermal sleeve 53 by a small annular space 54. At least a portion of the space 54 is filled with a heat insulating material 55 to prevent undue temperature differences from occurring in the thermal sleeve 53.
  • the small annular space 54 also communicates with a source (not shown) of a purge fluid, preferably steam.
  • Hydrocarbon delivery conduit 81 is equipped with an expansion joint 80 to compensate for the thermal expansion in the conduit.
  • At the outlet end of hydrocarbon delivery conduits 81 is an inlet nozzle 82 which, in the depicted embodiment, is connected to conduit 81 by threaded connection.
  • the inlet nozzle is preferably beveled or slanted with the beveled surface having a positive slope in the direction of flow of the superheated steam. More importantly, as depicted in more detail in Fig. 7, the inlet nozzle is aerodynamically shaped, e.g., as a teardrop. The more rounded end of the nozzle 82 faces the inlet of the superheated steam while the more pointed end faces the outlet of the hydrocarbon/superheated steam mixture.
  • the inlet for the superheated steam is preferably constricted to increase flow rates of the superheated steam as it flows past the inlet for the hydrocarbon.
  • the purge fluid is flowed through the insulation material 55. Since the purge fluid maintains a positive pressure in annular space 54, leakage of hydrocarbon and/or steam from bore 15 through the connection of inlet nozzle 82 and conduit 81 is prevented. The purge fluid also assists in carrying off convection heat in thermal sleeve 53.
  • the hydrocarbon from heat recovery furnace F flows through conduit 81 and exits from inlet nozzle 82 to be mixed with superheated steam flowing through bore 15.
  • the turbulence set up by the flow of the superheated steam provides immediate mixing of the steam and hydrocarbon. This mixing helps to prevent overheating of the reaction product, and it also helps to retard formation of degradation products such as methane and coke.
  • a further significant advantage of this mixing device structure is that the hydrocarbon is prevented from striking upon the wall of the reactor conduit where catalytically decomposition to form coke deposits is most probable.
  • a distinct advantage of the invention over other known processes is that a wide variety of hydrocarbon oils or gases may be employed as the hydrocarbon feed.
  • the usual feeds are broadly classified as light hydrocarbons, such as ethane, propane, butane and naphtha; and heavy hydrocarbons, such as kerosene, gas oil and vacuum gas oil.
  • light hydrocarbons such as ethane, propane, butane and naphtha
  • heavy hydrocarbons such as kerosene, gas oil and vacuum gas oil.
  • the data for each example was obtained by reacting a hydrocarbon feed in a laboratory apparatus which simulates actual operating conditions present in a production-size furnace used for thermal cracking of hydrocarbon feeds.
  • the product yield in each example is the result of a once-through run of the hydrocarbon feed.
  • the hydrocarbon feed was a propane composition.
  • the following data for this example relates to (1) the composition of the feed, (2) the process conditions for the reaction, and (3) the product yield obtained.
  • the hydrocarbon feed was a butane composition.
  • the data relating to feed composition, process conditions, and product yields is as follows:
  • the hydrocarbon feed was a naphtha composition.
  • Data relating to feed composition, feed properties, process conditions, and product yield is as follows:
  • the hydrocarbon feed was a naphtha composition.
  • Data relating to feed composition, feed properties, process conditions, and product yield is as follows:
  • the hydrocarbon feed was a naphtha composition.
  • Data relating to feed composition, feed properties, process conditions, and product yield is as follows:
  • the hydrocarbon feed was a vacuum gas oil composition.
  • Data relating to feed properties, process conditions and product yield is as follows:

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Claims (31)

1. Ein Verfahren zum Spalten von Kohlenwasserstoffen, in welchem eine Kohlenwasserstoff/supererhitzte Dampfmischung durch eine Reaktionszone geleitet wird und auf eine Temperatur gebracht wird, die ausreicht, um Kohlenwasserstoff zu spalten und anschlißend der gespaltene Kohlenwasserstoff von der Reaktionszone in einem Wärmeaustauscher geleitet wird, um das gespaltene Reaktionsprodukt abzuschrecken, dadurch gekennzeichnet, daß in der Reaktionszone die Kohlenwasserstoff/supererhitzte Dampfmischung durch eine Reaktionsleitung strömt, die sich durch eine Radiationsblockstruktur erstreckt, welche einen Durchlaß für die Reaktorleitung und Zwischenräume zwischen der Reaktorleitung und der inneren Oberfläche der Radiationsblockstruktur bildet, die es den Heizgasen erlaubt, durch die Radiationsblockstruktur in der gleichen Richtung, in der auch der Kohlenwasserstoff durch die Reaktionsleitung fließt, zu strömen.
2. Ein Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Kohlenwasserstoff in Form von Dampf oder feinem Nebel mit supererhitztem Dampf gemischt wird und die Mischung aus Kohlenwasserstoff und supererhitztem Dampf durch die Reaktorleitung geleitet wird.
3. Ein Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Kohlenwasserstoff auf bis 700°C oder dergleichen vorerhitzt ist, ohne daß eine signifikante Spaltung stattfindet und daß vor oder während des Vorerwärmens der Kohlenwasserstoff mit nicht mehr als 70 Gew.-%, bezogen auf das Gewicht des Kohlenwasserstoffes, des Wassers oder Dampfes gemischt ist.
4. Ein Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der Kohlenwasserstoff mit flüssigem Wasser vermischt ist.
5. Ein Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der supererhitzte Dampf, der mit dem Kohlenwasserstoff vermischt werden soll, dadurch hergestellt wird, daß der Dampf durch ein Rohr geleitet wird, welches von einer Radiationsblockstruktur umgeben und in ihr gelagert ist, und daß die Radiationsblockstruktur einen Durchlaß aufweist, der einen Gasfluß um wenigstens einen Teil der Dampfleitung erlaubt und daß der Dampf dadurch erhitzt wird, daß Heizgase durch den Durchlaß, der die Dampfleitung in der Radiationsblockstruktur umgibt, geleitet werden.
6. Ein Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der supererhitzte Dampf, der mit dem zugeführten Kohlenwasserstoff gemischt wird, eine Temperatur von 1000 bis 1500°C aufweist.
7. Ein Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß der supererhitzte Dampf, mit dem der zugemischte Kohlenwasserstoff gemischt wird, eine Temperatur von 1100 bis 1400°C aufweist.
8. Ein Verfahren nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, daß die Länge der zur Herstellung des supererhitzten Dampfes verwendeten Dampfleitung ausreichend kurz ist, daß der Druckabfall des Dampfes beim Durchleiten durch die Dampfleitung nicht höher als 4 Atmosphären beträgt.
9. Ein Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Dampfleitung weniger als 30 m lang ist.
10. Ein Verfahren nach einem der Ansprüche 1 bis 9, bei welchem der supererhitzte Dampf und der Kohlenwasserstoff in einer Mischvorrichtung gemischt werden, gekennzeichnet durch einen Einlaß für den supererhitzten Dampf, einen Einlaß für den Kohlenwasserstoff und einen Auslaß für die Mischung des Kohlenwasserstoffes und des Dampfes, wobei der Dampfeinlaß und der Auslaß für die Dampf/Kohlenwasserstoffmischung dermaßen angeordnet sind, daß der Dampf und die Mischung aus Dampf und Kohlenwasserstoff in die gleiche Richtung strömen können, der Einlaß für den Kohlenwasserstoff transversal zu dieser Richtung ist, der Einlaß für den Kohlenwasserstoff in einer aerodynamisch geformten Einlaßdüse endet, die eine eher runde Oberfläche aufweist, die dem Einlaß des supererhitzten Dampfes gegenübersteht und einer mehr zugespitzten Oberfläche, die dem Auslaß gegenübersteht, aus dem die Mischung aus Kohlenwasserstoff und supererhitztem Dampf in den supererhitzten Dampf eintritt.
11. Ein Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß die Einlaßdüse der Mischvorrichtung in Richtung des Flußes des supererhitzten Dampfes abgeschrägt ist, wobei die abgeschrägte Oberfläche eine positive Neigung in die Flußrichtung des supererhitzten Dampfes aufweist.
12. Ein Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß der Kohlenwasserstoffeinlaß der Mischvorrichtung mit einer Wärmeisolierungshülle versehen ist, die gegebenenfalls wenigstens teilweise mit einem Isolationsmaterial gefüllt ist, durch welche eine Reinigungs- und Kühlflüssigkeit geleitet werden kann.
13. Ein Verfharen nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß das Gewichtsverhältnis des supererhitzten Dampfes und der Kohlenwasserstoffbeschickung von 1:1 bis 2:1 reicht.
14. Ein Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß separat ein leichter Kohlenwasserstoff und ein schwerer Kohlenwasserstoff zugeführt werden kann, wobei die leichte anschließende Kohlenwasserstoffbeschickung auf eine Temperatur von 500 bis 700°C vorgeheizt wird und mit dem superheißen Dampf gemischt wird, unf die schwerere Beschickung auf eine Temperatur von 300 bis 500°C vorgeheizt und mit dem superheißen Dampf strömungsabwärts der besagten ersten Mischungsvorrichtung gemischt wird.
15. Ein Verfahren nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß vor oder während des Vorerhitzens eine leichte Kohlenwasserstoffbeschickung, die im wesentlichen Kohlenwasserstoffe von 5 Kohlenstoffatomen oder weniger enthält, mit 0 bis 20 Gew.-% Wasser gemischt wird und eine schwere Kohlenwasserstoffbeschickung, die im wesentlichen Kohlenwasserstoffe mit 6 oder mehr Kohlenstoffatomen enthält, mit 10 bis 70 Gew.-% Wasser gemischt wird.
16. Ein Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß die Verweildauer in der Reaktionsröhre bei der Beschickung von leichtem Kohlenwasserstoff auf 0,06 bis 0,15 Sekunden und bei der Beschickung mit schweren Kohlenwasserstoffen auf 0,005 bis 0,08 Sekunden eingestellt wird.
17. Ein Verfahren nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, daß der Druckabfall auf dem Weg zwischen dem Anfangspunkt des Systems, in welchem der superheiße Dampf hergestellt wird und dem Austritt aus dem Wärmeaustauscher nicht mehr als 4 Atmosphären beträgt.
18. Ein Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, daß die Reaktionsröhre weniger als 15 m lang ist.
19. Ein Verfahren nach einem der Ansprüche 1 bis 18, dadurch gekennzeichnet, daß eine Radiationsblockstruktur verwendet wird, die eine Vielzahl von Keramikradiationsblocks umfaßt, welche so angeordnet sind, daß sie aneinander anstoßen und dabei einen inneren verlängerten Durchlaß für die Reaktorleitung oder die superheiße Dampfleitung bildet, und der besagte Durchlaß mindestens eine Halterung für die Reaktor- oder superheiße Dampfleitung bildet und eine vergrößerte Oberfläche bildet, um die Strahlungswärme für die besagten Leitungen .zu liefern.
20. Ein Verfahren nach Anspruch 19, gekennzeichnet durch die Verwendung von Radiationsblocks, deren Durchlässe im Querschnitt die Form eines vierblättrigen Kleeblattes aufweisen, und die Leitung von wenigstens einem der inneren Schultern gehalten wird und sich, bezogen auf die anderen Schultern, frei hält.
21. Ein Verfahren nach Anspruch 19, gekennzeichnet durch die Verwendung von Radiationsblocks, deren Durchlässe im Querschnitt eine vierfache Helixstruktur aufweisen, wobei die Leitung mit einem Abstand von den Schultern gelagert ist.
22. Ein Verfahren nach einem der Ansprüche 1 bis 21, dadurch gekennzeichnet, daß die Kohlenwasserstoffbeschickung mit Heizgas auf eine Temperatur von bis zu 700°C vorgeheizt wird, wobei aber die Temperatur so gewählt ist, daß keine signifikante Mengen der Kohlenwasserstoffbeschickung gespalten wird.
23. Ein Verfahren nach einem der Ansprüche 1 bis 22, dadurch gekennzeichnet, daß wenn notwendig, eine Reinigungsvorgang mit superheißem Dampf dadurch durchgeführt wird, daß die Kohlenwasserstoffbeschickung der Mischvorrichtung und der Zufluß von Kühlflüssigkeit zum Wärmeaustauscher unterbrochen wird.
24. Eine Vorrichtung zum Spalten von Kohlenwasserstoffen, gekennzeichnet durch eine Vorrichtung zur Herstellung von superheißem Dampf, eine Mischvorrichtung zum Mischen von Kohlenwasserstoffen mit dem superheißen Dampf, eine Reaktorleitung, durch welche die Mischung von Kohlenwasserstoff und superheißem Dampf strömen kann, wobei die besagte Reaktorleitung durch eine Radiationsblockstruktur reicht, welche einen Durchgang bildet, durch den Gase wenigstens um einen Teil der Reaktorleitung strömen können, eine Vorrichtung zum Erhitzten der Mischung von Kohlenwasserstoff und supererhitztem Dampf, die den Fluß des Heizgases durch die Radiationsblockstruktur liefert und einen Wärmeaustauscher zum Abschrecken des heißen Reaktionsproduktes.
25. Eine Vorrichtung nach Anspruch 24, gekennzeichnet durch eine Reaktorleitung aus keramischem Material.
26. Eine Vorrichtung nach Anspruch 25, dadurch gekennzeichnet, daß die keramische Reaktorleitung transparent oder durchscheinend ist.
27. Eine Radiationsblockstruktur, geeignet für die Verwendung in den Verfahren nach einem der Ansprüche 1 bis 23, gekennzeichnet durch eine Vielzahl von aneinanderstoßenden Blocks aus keramischem Material, die
a) einen verlängerten Durchlaß bilden, der eine Öffnung enthält, durch welche eine Leitung laufen kann und
b) offene Zwischenräume in Verbindung mit der besagten Öffnung aufweist und die besagten Zwischenräume eine solche Form haben, daß sie einen Durchlaß für ein Gas bilden.
28. Radiationsblocks nach Anspruch 27, dadurch gekennzeichnet, daß die offenen Zwischenräume im Querschnitt die Form eines vierblättrigen Kleeblattes aufweisen.
29. Radiationsblocks nach Anspruch 27, dadurch gekennzeichnet, daß die offenen Räume im Querschnitt die Form einer vierfachen Helixstruktur aufweisen.
30. Ein Verfahren nach einem der Ansprüche 1 bis 23, dadurch gekennzeichnet, daß eine Kohlenwasserstoff/superheiße Dampfmischung bei ihrem Durchfluß durch die Reaktorleitung so erhitzt wird, daß der Wärmefluß zum Kohlenwasserstoff kontinuierlich so herabgesetzt wird, wie das Spalten fortschreitet.
31. Eine Vorrichtung nach einem der Ansprüche 24 bis 26, gekennzeichnet durch eine Reaktorleitung (34), die durch eine Radiationsblockstruktur (35) aus keramischem Material reicht, welche einen Verlängerungsdurchlaß (41) bildet, und der Durchlaß
a) eine Öffnung aufweist, durch welche eine Leitung gelegt werden kann und
b) offene Räume in Verbindung mit der besagten Leitungsöffnung aufweist, wobei die besagten Räume eine solche Konfiguration aufweisen, daß sie einen Durchlaß für ein Gas bilden und eine Vorrichtung (37) zum Erhitzen des Kohlenwasserstoffes durch Heizgase in der Radiationsblockstruktur (35).
EP81201000A 1981-09-08 1981-09-08 Verfahren und Apparat zur Kohlenwasserstoffspaltung; Mischanlage; Apparat und Verfahren zur Produktion von überhitztem Dampf; Radiationblockstruktur Expired EP0074435B1 (de)

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EP81201000A EP0074435B1 (de) 1981-09-08 1981-09-08 Verfahren und Apparat zur Kohlenwasserstoffspaltung; Mischanlage; Apparat und Verfahren zur Produktion von überhitztem Dampf; Radiationblockstruktur
DE8181201000T DE3173374D1 (en) 1981-09-08 1981-09-08 Process and apparatus for cracking hydrocarbon; mixing device; apparatus and process for producing superheated steam; radiation block structure
US06/405,212 US4426278A (en) 1981-09-08 1982-08-04 Process and apparatus for thermally cracking hydrocarbons
CA000423303A CA1207266A (en) 1981-09-08 1983-03-10 Process and apparatus for thermally cracking hydrocarbons
JP58044584A JPS59170187A (ja) 1981-09-08 1983-03-18 炭化水素熱分解方法及び装置
AU12624/83A AU556528B2 (en) 1981-09-08 1983-03-21 Process and apparatus for thermally cracking hydrocarbons

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AU1262483A (en) 1984-09-27
US4426278A (en) 1984-01-17
DE3173374D1 (en) 1986-02-13
JPS59170187A (ja) 1984-09-26
EP0074435A2 (de) 1983-03-23
AU556528B2 (en) 1986-11-06
EP0074435A3 (en) 1983-05-04
JPS6410036B2 (de) 1989-02-21
CA1207266A (en) 1986-07-08

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